Metathesis is generally thought of as the interchange of radicals between two compounds during a chemical reaction. There are several varieties of metathesis reactions, such as ring opening metathesis, acyclic diene metathesis, ring closing metathesis, and cross metathesis. These reactions, however, have had limited success with the metathesis of functionalized olefins.
Methods for the production of polyolefins with end-functionalized groups are typically multi-step processes that often create unwanted by-products and waste of reactants and energy.
R. T. Mathers and G. W. Coates Chem. Commun., 2004, pp. 422-423 disclose examples of using cross-metathesis to functionalize polyolefins containing pendant vinyl groups to form polar-functionalized products with a graft-type structure.
D. Astruc et al. J. Am. Chem. Soc. 2008, 130, pp. 1495-1506, and D. Astruc et al. Angew. Chem. Int. Ed., 2005, 44, pp. 7399-7404 disclose examples of using cross metathesis to functionalize non-polymeric molecules containing vinyl groups.
For reviews of methods to form end-functionalized polyolefins, see: (a) S. B. Amin and T. J. Marks, Angew. Chem. Int. Ed., 2008, 47, pp. 2006-2025; (b) T. C. Chung Prog. Polym. Sci., 2002, 27, pp. 39-85; and (c) R. G. Lopez, F. D′Agosto, C. Boisson Prog. Polym. Sci., 2007, 32, pp. 419-454.
U.S. Ser. No. 12/487,739, filed Jun. 19, 2009 discloses certain vinyl terminated oligomers and polymers that are functionalized, optionally, for use in lubricant applications.
U.S. Ser. No. 12/143,663, filed on Jun. 20, 2008 discloses certain vinyl terminated oligomers and polymers that are functionalized in U.S. Ser. No. 12/487,739, filed Jun. 19, 2009. U.S. Pat. No. 8,283,428 and U.S. Ser. No. 13/629,323, filed Sep. 27, 2012, which are incorporated by reference herein, provide polymacromonomers useful for functionalization.
U.S. Ser. No. 12/488,093, filed Jun. 19, 2009 discloses end functionalized polyolefins prepared from vinyl terminated polyolefins by cross metathesis.
Additional references of interest include U.S. Pat. Nos. 4,988,764; 6,225,432; 6,111,027; 7,183,359; 6,100,224; 5,616,153; PCT Publication Nos. WO 03/025084; WO 03/025038; WO 03/025037; WO 03/025036; WO 99/016845 and Amelia M. Anderson-Wilfe et al., “Synthesis and Ring-Opening Metathesis Polymerization of Norbornene-Terminated Syndiotactic Polypropylene”, Macromolecules, 2012, 45 (19), pp. 7863-7877, published (web) Sep. 19, 2012.
Thus, metathesis reactions can provide functionalized polyolefins that have end-functionalization. However, to date it has not been feasible to polymerize polyolefins having end-functionalization to each other.
Thus, a need exists for a method to prepare polyolefins that utilize end-functionalization to provide new polymers with unique physical properties.